CN110078054B - Preparation method and application of graphene-carbon nanotube three-dimensional compound - Google Patents
Preparation method and application of graphene-carbon nanotube three-dimensional compound Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a graphene-carbon nanotube three-dimensional compound, wherein the compound can be applied to the construction of a selective ultrafast photoelectric detector, and can realize ultraviolet-visible-near infrared multiband high-sensitivity ultrafast detection through the detection difference value of a main unit and a base unit which are strongly absorbed by each waveband; the detection switches of the main units are regulated and controlled through grid voltage, and switching detection of ultraviolet, visible and near-infrared bands is achieved. In addition, the graphene-carbon nanotube three-dimensional composite is also a heat conducting material, and the three-dimensional transmission channel of the graphene-carbon nanotube three-dimensional composite can obviously improve the heat dissipation efficiency of the device and prolong the service life of the device.
Description
Technical Field
The invention belongs to the technical field of composites, and particularly relates to a preparation method and application of a graphene-carbon nanotube three-dimensional composite.
Background
The high-temperature catalytic cracking chemical vapor deposition method can grow a carbon nanotube array which is vertical to the surface of the substrate and grows directionally, and a graphene-carbon nanotube three-dimensional compound of which the top end of the carbon nanotube array is covered with a layer of graphene film. During the growth process, argon is a protective gas, hydrogen is a reducing gas, and phthalocyanine iron (FeC 32N8H 16) is the only chemical agent for growing the carbon nanotubes and the graphene-carbon nanotube three-dimensional compound, and is used as a carbon source supply and a catalyst supply. The ratio of the number of iron atoms to the number of carbon atoms in the chemical formula of the phthalocyanine iron is 1. At 550 ℃, phthalocyanine iron begins to sublimate, and gradually drifts to a high-temperature growth temperature zone of 900 ℃ along with the airflow under the protection of inert gas argon. Meanwhile, in the drifting process, phthalocyanine iron is continuously cracked into carbon atoms and iron atoms, then the carbon atoms descend in air flow and adhere to the silicon substrate, and finally, under the action of reducing gas hydrogen and catalyst iron atoms, carbon is precipitated in a tube form and continuously grows into carbon nanotubes from bottom to top. The growth mode of the carbon nano tube is a bottom growth mechanism from bottom to top. The adhesion force between the iron ions of the catalyst and the surface of the silicon substrate is strong, and carbon is separated from the surface of the iron ions in a tubular form and continuously grows upwards, so that the bottom growth model mechanism is formed. In the regrowth process, hydrogen is used as reducing gas to participate in the growth of the carbon nano tube, so that the growth of the carbon nano tube is greatly influenced, and the tip appearance of the carbon nano tube is directly influenced. Experimentally, when the hydrogen flow is less than 30sccm, a three-dimensional composite of the carbon nanotube and the graphene is grown; when the hydrogen flow is more than or equal to 30sccm, a carbon nanotube array is grown. The hydrogen flow rate is referenced to 10sccm, and as the gas flow rate increases to 30sccm, the graphene sheets at the tips of the carbon nanotube array gradually decrease until there are no graphene sheets. However, when the hydrogen flow is increased to more than 30sccm, the carbon nanotube array is not changed in shape, but the carbon nanotubes are blown down by the excessive flow of the hydrogen and the argon. Theoretically, when the hydrogen flow rate is too small, after hydrogen gas reduces carbon in the phthalocyanine iron, hydrogen gas is insufficient, it is difficult to completely open the carbon ring in the phthalocyanine iron, and carbon cannot exist in the form of carbon atoms but exists in the form of a carbon ring to form graphene. If the hydrogen flow is further reduced, less carbon is reduced, the growth of carbon nanotubes is affected, and more graphite sheets with thicker layers are produced; when the hydrogen flow rate was increased, the carbon in the phthalocyanine iron was reduced to metastable carbon atoms, which grew in tubular form into carbon nanotubes. Therefore, when the hydrogen flow is 28sccm-35sccm, the grown carbon nanotube array is best vertically and directionally grown, uniformly distributed, consistent in height and high in purity; when the hydrogen flow is between 8sccm and 13sccm, the grown carbon nanotube-graphene composite is preferably formed by covering the top end of the vertically oriented carbon nanotube array with a graphene film to completely cover the tip end of the carbon nanotube array.
Disclosure of Invention
The invention aims to provide a preparation method and application of a graphene-carbon nanotube three-dimensional compound based on technical background.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the graphene-carbon nanotube three-dimensional compound is characterized by comprising the following steps of:
step 1: preparation of the chemical phthalocyanine iron and growth substrate: cutting a growth substrate silicon wafer, ultrasonically cleaning the silicon wafer in acetone, ethanol and deionized water, drying the silicon wafer, placing the silicon wafer on a quartz boat, and then placing phthalocyanine iron powder on the silicon wafer substrate;
step 2: the quartz boat is arranged in the reaction chamber of the quartz tube: pushing the quartz boat to the edge of the heating furnace to prevent the phthalocyanine iron from being pushed into the heating furnace to sublimate in advance;
and step 3: introducing argon and starting heating: opening a protective gas argon gas cylinder valve, opening a gas flow instrument to set the protective gas argon gas cylinder valve to be 60sccm, starting to heat the heating furnace, wherein the target temperature is 900 ℃, and the heating rate is set to be 0.5 ℃/s;
and 4, step 4: introducing hydrogen: opening a valve of a hydrogen gas bottle, setting the hydrogen flow of a gas flowmeter to be 10sccm, wherein at the moment, the phthalocyanine iron does not reach the sublimation temperature at the pipe orifice of the heating furnace, moving the phthalocyanine iron to a sublimation temperature area after the hydrogen in the pipe is filled in the whole quartz pipe, and beginning sublimation of the phthalocyanine iron after the hydrogen completely reaches a silicon substrate growth area, so that the next operation is started after the hydrogen is introduced for 10 minutes;
and 5: moving the quartz boat to a growth temperature region: the quartz tube is pushed at the speed of 1cm/min, phthalocyanine iron can be seen to be sublimated into black green gas in the pushing process, and the temperature in the furnace is slightly reduced;
step 6: growing the graphene-carbon nanotube three-dimensional compound: after the quartz tube is pushed, phthalocyanine iron is in a high-temperature area in the furnace at the moment, is rapidly sublimated, cracked and vaporized, a silicon wafer substrate is also in a growth temperature area, a carbon nano tube array starts to grow on the silicon wafer substrate under the action of reducing hydrogen and catalyst iron particles, when hydrogen is continuously consumed and insufficient in the growth process, a graphene layer starts to be formed at the top end of the carbon nano tube array, and the whole growth process lasts for 15 minutes; after 15 minutes, the hydrogen was turned off and the heating was stopped;
and 7: cooling: gradually cooling the furnace under the protection of argon, naturally cooling the furnace for 3 hours to room temperature, and still introducing protective gas argon in the whole process of cooling the furnace to prevent the graphene-carbon nanotube three-dimensional compound from being oxidized at high temperature;
and 8: taking out the graphene-carbon nanotube three-dimensional compound: and when the heating furnace is cooled to room temperature, closing the argon and the gas flowmeter, opening the gas inlet end of the quartz tube, pulling out the quartz boat, and then, observing that the silicon substrate on the quartz boat is changed into grey white, wherein the grey white is the graphene-carbon nanotube three-dimensional compound. Carbon nanotubes are black, the fewer the number of graphene layers, the lighter the color, and the single layer graphene is only one atomic layer thick and invisible to the naked eye. The three-dimensional compound grown by the method is formed by covering the top end of the carbon nanotube with a layer of graphene, and the covered graphene is a multilayer graphene, so that the color of the compound is grey white instead of black.
Further, in step 1, the ultrasonic cleaning time is 10 minutes, and the phthalocyanine iron powder is arranged into a square of 2 x 2cm2 and is arranged between 2cm and 8cm away from the edge of the silicon wafer substrate.
Further, in step 3, the holding time in the heating furnace is set to 150 minutes, wherein the temperature in the heating furnace reaches 900 ℃, the temperature is raised at the rate of 0.5 ℃/s, 30 minutes are required, in order to make the temperature more stable and continue for 20 minutes, and the time of the growth time, experimental factors such as instruments and human factors, and the holding time in the furnace is at least 110 minutes, and in order to have sufficient time and suitable growth environment, the holding time in the heating furnace is set to be 150 minutes optimally.
Further, the quartz tube was advanced by 6 cm in step 5 so that both the phthalocyanine iron and the silicon substrate were within the specified position area.
Furthermore, the heating furnace is heated by a temperature control system.
Further, in the step 8, after the silicon wafer on which the graphene-carbon nanotube three-dimensional compound grows is taken down by using tweezers, the quartz boat is cleaned by using an alcohol cotton ball, placed at a specified position, and the test bed and the instrument and equipment are cleaned.
The application of the graphene-carbon nanotube three-dimensional compound is characterized in that: the graphene-carbon nanotube three-dimensional compound is applied to an ultrafast photoelectric detector.
Further, the compound is a 3D transmission channel of a carrier, and the transmission channel is also three-dimensional transmission [ Wei 1] of a hot carrier; the compound is a light absorption material, and graphene-carbon nanotubes are modified by nanocrystalline grains with strong absorption at different wave bands so as to increase the absorption difference of each wave band; then preparing an ultraviolet, visible and near-infrared band selective strong absorption array unit of the FET structure, and finally integrating all band detection units on the same silicon substrate.
Due to the preparation method and the application of the graphene-carbon nanotube three-dimensional compound, the following beneficial effects can be obtained:
the compound is grown on a silicon dioxide substrate or a silicon wafer substrate by adopting a high-temperature catalytic cracking chemical vapor deposition method, and the compound has the advantages of simple process and easy operation. The process method is characterized in that the graphene-carbon nanotube three-dimensional compound is grown by changing the gas flow of hydrogen. The grown carbon nanotube is multi-walled carbon nanotube, grows vertically, uniformly and directionally, has a height of 6-10 μm, and has a single carbon tube diameter of 20-100 nm. The grown graphene is a multilayer graphene film.
The compound can be applied to a selective ultrafast photoelectric detector, and can realize ultraviolet-visible-near infrared multiband high-sensitivity ultrafast detection through the detection difference value of each waveband strong absorption main unit and a base unit; the detection switches of the main units are regulated and controlled through grid voltage, and switching detection of ultraviolet, visible and near-infrared bands is achieved. In addition, the graphene-carbon nanotube three-dimensional composite is also a heat conducting material, and the three-dimensional transmission channel of the graphene-carbon nanotube three-dimensional composite can obviously improve the heat dissipation efficiency of the device and prolong the service life of the device.
Drawings
The present invention is described in further detail below with reference to the attached drawings.
Fig. 1 is a raman spectrum of a carbon nanotube array.
Fig. 2 is a raman spectrum of the graphene-carbon nanotube three-dimensional composite.
FIG. 3 is a top view of the carbon nanotube array at a flow rate of 30sccm hydrogen and a flow rate of 60sccm argon.
FIG. 4 is a side view of the carbon nanotube array at a flow rate of hydrogen of 30sccm and an argon flow of 60sccm.
FIG. 5 is a top view of the graphene-carbon nanotube three-dimensional composite when the hydrogen flow rate is reduced to 10sccm.
FIG. 6 is a side view of the graphene-carbon nanotube three-dimensional composite when the hydrogen flow rate is reduced to 10sccm.
Fig. 7 is a schematic diagram of a uv-vis-nir selective ultrafast photodetector structure.
FIG. 8 is a schematic of the electrical and thermal transport mechanism of the composite.
Detailed Description
The invention is further described below with reference to the accompanying drawings:
as shown in fig. 1 to 3, the method for preparing the graphene-carbon nanotube three-dimensional composite is characterized by comprising the following steps:
step 1: preparation of the chemical phthalocyanine iron and growth substrate: cutting a growth substrate silicon wafer, ultrasonically cleaning the silicon wafer in acetone, ethanol and deionized water, drying the silicon wafer, placing the silicon wafer on a quartz boat, and then placing phthalocyanine iron powder on the silicon wafer substrate;
step 2: the quartz boat is arranged in the reaction chamber of the quartz tube: pushing the quartz boat to the edge of the heating furnace to prevent the phthalocyanine iron from being pushed into the heating furnace to sublimate in advance;
and step 3: introducing argon and starting heating: opening a protective gas argon gas cylinder valve, opening a gas flow instrument to set the protective gas argon gas cylinder valve to be 60sccm, starting to heat the heating furnace, wherein the target temperature is 900 ℃, and the heating rate is set to be 0.5 ℃/s;
and 4, step 4: introducing hydrogen: opening a valve of a hydrogen gas bottle, setting the hydrogen flow of a gas flowmeter to be 10sccm, wherein at the moment, the phthalocyanine iron does not reach the sublimation temperature at the pipe orifice of the heating furnace, moving the phthalocyanine iron to a sublimation temperature area after the hydrogen in the pipe is filled in the whole quartz pipe, and beginning sublimation of the phthalocyanine iron after the hydrogen completely reaches a silicon substrate growth area, so that the next operation is started after the hydrogen is introduced for 10 minutes;
and 5: moving the quartz boat to a growth temperature region: the quartz tube is pushed at the speed of 1cm/min, phthalocyanine iron can be seen to be sublimated into black green gas in the pushing process, and the temperature in the furnace is slightly reduced;
step 6: growing the graphene-carbon nanotube three-dimensional compound: after the quartz tube is pushed, phthalocyanine iron is in a high-temperature area in the furnace at the moment, is rapidly sublimated, cracked and vaporized, a silicon wafer substrate is also in a growth temperature area, a carbon nano tube array starts to grow on the silicon wafer substrate under the action of reducing hydrogen and catalyst iron particles, when hydrogen is continuously consumed and insufficient in the growth process, a graphene layer is formed at the top end of the carbon nano tube array, and the whole growth process lasts for 15 minutes. After 15 minutes, the hydrogen was turned off and the heating was stopped;
and 7: cooling: gradually cooling the furnace under the protection of argon, naturally cooling the furnace for 3 hours to room temperature, and still introducing protective gas argon in the whole process of cooling the furnace to prevent the graphene-carbon nanotube three-dimensional compound from being oxidized at high temperature;
and 8: taking out the graphene-carbon nanotube three-dimensional compound: and when the heating furnace is cooled to room temperature, closing the argon and the gas flowmeter, opening the gas inlet end of the quartz tube, pulling out the quartz boat, and then, observing that the silicon substrate on the quartz boat is changed into grey white, wherein the grey white is the graphene-carbon nanotube three-dimensional compound. Carbon nanotubes are black, the fewer the number of graphene layers, the lighter the color, and the single layer graphene is only one atomic layer thick and invisible to the naked eye. The three-dimensional compound grown by the method is formed by covering the top end of the carbon nanotube with a layer of graphene, and the covered graphene is a multilayer graphene, so that the color of the compound is grey white instead of black.
In the step 1, the ultrasonic cleaning time is 10 minutes, and phthalocyanine powder is arranged in a square of 2 multiplied by 2cm2 and is arranged between 2cm and 8cm away from the edge of the silicon wafer substrate.
In step 3, the holding time in the heating furnace is set to 150 minutes, wherein the temperature in the heating furnace reaches 900 ℃, the temperature is increased at the rate of 0.5 ℃/s, the holding time is 30 minutes, the holding time in the heating furnace is at least 110 minutes for more stable temperature and further 20 minutes, the growth time is added, and the time of experimental factors such as instruments, human beings and the like is prolonged, and the holding time in the heating furnace is set to be 150 minutes optimally for sufficient time and suitable growth environment.
The quartz tube was advanced 6 cm in step 5 so that both the phthalocyanine iron and the silicon substrate were within the specified location area.
The heating furnace is heated by a temperature control system.
And 8, taking down the silicon wafer on which the graphene-carbon nanotube three-dimensional compound grows by using tweezers, cleaning the quartz boat by using an alcohol cotton ball, placing the quartz boat in a specified position, and cleaning the test bed and the instrument and equipment.
The application of the graphene-carbon nanotube three-dimensional compound is characterized in that: the graphene-carbon nanotube three-dimensional compound is applied to a constructive ultrafast photoelectric detector.
The compound is a light absorption material and a 3D transmission channel of a current carrier, and the graphene-carbon nano tube is modified with nanocrystalline grains with strong absorption at different wave bands so as to increase the absorption difference of each wave band; then preparing an ultraviolet, visible and near-infrared band selective strong absorption array unit of the FET structure, and finally integrating all band detection units on the same silicon substrate. In addition, the graphene-carbon nanotube three-dimensional composite is also a heat conducting material, and the three-dimensional transmission channel of the graphene-carbon nanotube three-dimensional composite can obviously improve the heat dissipation efficiency of the device and prolong the service life of the device.
The working principle and the working process of the invention are as follows:
the specific operation is as follows:
1) Preparation of experimental reagents, iron phthalocyanine and growth substrate:
and cutting the substrate silicon wafer into required size. Ultrasonic cleaning in acetone, ethanol and deionized water for 10 minutes respectively, and then drying and placing the silicon wafer on a quartz boat. And then, the phthalocyanine powder is regulated into a square of 2 multiplied by 2cm & lt 2 & gt, and the distance between the phthalocyanine powder and the edge of the silicon wafer substrate is 2cm-8 cm.
2) The quartz boat is placed in a quartz tube reaction chamber:
and opening the gas inlet end of the quartz tube, placing the quartz boat in the quartz tube, pushing the quartz boat to the most edge of the heating furnace by using the quartz hook, and finally closing the gas inlet end of the quartz tube. When pushing the quartz boat, the quartz boat is pushed to the edge of the heating furnace. It must not be possible to push the phthalocyanine iron into the furnace, preventing it from sublimating in advance.
3) Introducing argon and starting heating:
the protective gas argon cylinder valve was opened and the gas flow meter was set to 60sccm. Then, a heating furnace temperature control system is started to set the temperature to 900 ℃, the heating rate to 0.5 ℃/s, and the holding time to 150 minutes. The heating and temperature rising process is an important link, and a stable argon atmosphere is provided for the growth of the graphene-carbon nanotube three-dimensional compound. The temperature in the furnace reached 900 ℃ and was raised at a rate of 0.5 ℃/s for 30 minutes, and the hold time in the furnace was at least 110 minutes for a further 20 minutes duration to stabilize the temperature plus the growth time. And because the equipment needs a preparation response time for each setting process, in order to have sufficient time and a proper growing environment, the holding time in the heating furnace is set to be 150 minutes optimally.
4) Introducing hydrogen:
the hydrogen is a reducing gas in the growth process of the graphene-carbon nanotube three-dimensional compound. The valve of the hydrogen gas cylinder is opened, and the hydrogen flow of the gas flowmeter is set to be 10sccm. At this moment, phthalocyanine iron does not reach sublimation temperature at the mouth of pipe of heating furnace, treats that intraductal hydrogen is full of and removes phthalocyanine iron to sublimation warm area after whole quartz capsule again. It is necessary to ensure that after the hydrogen gas completely reached the silicon substrate growth area, the sublimation of phthalocyanine iron was resumed, so that the next operation was resumed 10 minutes after the hydrogen gas was introduced.
5) Moving the quartz boat to a growth temperature region:
after 10 minutes of hydrogen gas introduction, the quartz tube was advanced by 6 cm at a speed of 1 cm/min. During the run, it was observed that phthalocyanine iron sublimated into a dark green gas, and the temperature in the furnace decreased slightly. The quartz tube was advanced 1cm per minute to ensure the temperature field in the furnace was stable, and a total of 6 cm was advanced so that both the phthalocyanine iron and the silicon substrate were within the designated location area.
6) And (3) growing the graphene-carbon nanotube three-dimensional compound:
after the quartz tube is pushed, phthalocyanine iron is in a high-temperature area in the furnace at the moment, is rapidly sublimated, cracked and vaporized, a silicon wafer substrate is also in a growth temperature area, a carbon nano tube array starts to grow on the silicon wafer substrate under the action of reducing hydrogen and catalyst iron particles, when hydrogen is continuously consumed and insufficient in the growth process, a graphene layer is formed at the top end of the carbon nano tube array, and the whole growth process lasts for 15 minutes. After 15 minutes, the hydrogen was turned off and the heating was stopped;
7) Cooling: and after the heating furnace is turned off, gradually cooling the inside of the furnace under the protection of argon, and naturally cooling the inside of the furnace for 3 hours to room temperature. In the whole process of cooling the heating furnace, protective gas argon is still introduced to prevent the graphene-carbon nanotube ternary compound from being oxidized at high temperature.
8) Taking out the graphene-carbon nanotube three-dimensional compound:
and when the heating furnace is cooled to room temperature, closing the argon and the gas flowmeter, opening the gas inlet end of the quartz tube, pulling out the quartz boat, and then, observing that the silicon substrate on the quartz boat is changed into grey white, wherein the grey white is the graphene-carbon nanotube three-dimensional compound. Carbon nanotubes are black, the fewer the number of graphene layers, the lighter the color, and the single layer graphene is only one atomic layer thick and invisible to the naked eye. The three-dimensional compound grown by the method is formed by covering the top end of the carbon nanotube with a layer of graphene, and the covered graphene is a multilayer graphene, so that the color of the compound is grey white instead of black.
Carbon nanotube:
when the flow rate of hydrogen was 30sccm and the flow rate of argon was 60sccm, the grown carbon nanotube array was shown in the figure, in which (3) is a plan view of the carbon nanotube array and (4) is a side view.
Fig. 1 is a raman spectrum of a carbon nanotube array, the grown carbon nanotubes are multi-walled carbon nanotubes with a hollow middle, and the spacing between the carbon nanotube layers is 0.34nm, which is equivalent to the interlayer spacing of graphite, and this is also one of the typical characteristics of multi-walled carbon nanotubes. And the diameter of a single carbon tube of the grown carbon nanotube array is 20 nm-100 nm. As can be seen from the Raman spectrum, 1350cm -1 And 1580cm -1 Two characteristic peaks at (A), exactly two characteristic peaks of a multi-walled carbon nanotube, a D (Defects) peak and a G (Graphite) peak.
Graphene-carbon nanotube three-dimensional composites:
the hydrogen flow rate was reduced to 10sccm, and other conditions were unchanged, and the graphene-carbon nanotube three-dimensional composite was grown in the same manner, wherein fig. 5 is a top view and fig. 4 is a side view of the graphene-carbon nanotube three-dimensional composite. As a result, it was found that the grown graphene-carbon nanotube three-dimensional composite was grayish white, rather than the pure black seen before. Analysis of the microstructure by SEM microscope revealed that the carbon nanotube tips had a thin film covering the tips of the vertically oriented carbon nanotube array. However, in the whole experiment process of growing the carbon nanotubes, the raw material used was only phthalocyanine iron, and thus except that the carbon source was the catalyst iron, it was inferred that the carbon film covered on the top of the carbon nanotubes was a carbon film, i.e., a multilayer graphene film. Single layer graphene is a transparent, monoatomic layer film that cannot be seen with the naked eye. With the increase of the number of graphene layers, the color gradually deepens, and the black color is not formed until the graphite sheet is formed. Thus, a sheet-like film with grayish white top ends of carbon nanotubes is a multilayer graphene film.
The Raman spectrum is also one of effective methods for characterizing and analyzing the nano material. Whether the film at the top end of the carbon nano tube is a multilayer graphene film or not can be directly and effectively judged through the characteristic peak of the Raman spectrum. Fig. 2 is a raman spectrum of a graphene-carbon nanotube, a three-dimensional composite of graphene-carbon nanotube grown by pyrometallurgical pyrolysis chemical deposition of phthalocyanine iron. Wherein the length of the groove is 1350cm -1 And 1580cm -1 Two characteristic peaks of the carbon nanotube, D (Defects) peak and G (Grapite) peak. 2700cm -1 The corresponding peak is the characteristic peak 2D peak of the determined graphene. Therefore, it can be concluded that the off-white film of the carbon nanotube tips is a multilayer graphene thin film. The hydrogen flow rate was reduced to 10sccm and a graphene-carbon nanotube three-dimensional composite could be grown using this growth process.
The Raman spectrum of the carbon nanotube array in FIG. 1 has a characteristic peak of 1350cm as described in conjunction with FIGS. 1 and 2 -1 And 1580cm -1 Characteristic peaks of multi-walled carbon nanotubes. FIG. 2 is a Raman spectrum of a graphene-carbon nanotube three-dimensional composite, wherein the composite has two characteristic peaks of carbon nanotubes and a significant 2700cm -1 2D characteristic peak of graphene. 2700cm -1 Since the stronger the peak value, the smaller the number of graphene layers, the graphene is generally determined by the 2D characteristic peak.
Fig. 8 shows an ultra-fast photodetector with a novel structure and selectivity of ultraviolet-visible-near infrared. The method comprises the steps that a graphene-carbon nanotube three-dimensional (3D CNTs-G) compound is used as a light absorption material and a 3D transmission channel of a current carrier, and 3D CNTs-G is modified with nano crystal grains which are strongly absorbed at different wave bands, so that the absorption difference of each wave band is increased; then preparing an ultraviolet, visible and near-infrared band selective strong absorption array unit with an FET structure, and finally integrating all band detection units on the same silicon substrate. The array type multiband 3D CNTs-G optical detection can realize ultraviolet-visible-near infrared (UV-VIS-NIR) multiband high-sensitivity ultrafast detection through detection difference values of the main units and the base units with strong absorption of each waveband; the detection switches of the main units are regulated and controlled through grid voltage, and switching detection of ultraviolet, visible and near-infrared bands is achieved. In addition, the graphene-carbon nanotube three-dimensional composite is also a heat conducting material, and the three-dimensional transmission channel of the graphene-carbon nanotube three-dimensional composite can obviously improve the heat dissipation efficiency of the device and prolong the service life of the device.
The compound is a 3D structure nano material with G covered on the surface of the bush of CNTs, and the CNTs and the G are connected by chemical bonds. The in-situ grown 3D CNTs-G compound is different from the CNTs/G compound formed by a physical method. The transferred CNTs/G is a three-dimensional structure compound formed by bonding CNTs and G through van der Waals force adsorption. Therefore, the 3D CNTs-G grown in situ not only has excellent performances of ultrahigh electron mobility, thermal conductivity and the like of CNTs and G, but also has a unique 3D transmission channel, and can simultaneously carry out rapid carrier transmission in the transverse direction and the longitudinal direction. The rapid transmission of the carrier in the three-dimensional direction enables efficient and ultrafast photoelectric detection, and meanwhile, the heat dissipation problem of the photoelectric device is solved. Photovoltaic devices often develop hot spots due to the accumulation of light and heat, which can reduce the efficacy of the device or burn out the device. The 3D CNTs-G provides a rapid conveying channel in the three-dimensional direction for the photoelectric detector, avoids the aggregation of light and heat and the generation of hot spots, improves the heat dissipation characteristic of the device, and improves the working efficiency and the service life.
The carbon nanotube forest on the surface of the 3D compound can modify strong light absorption nanocrystalline grains with different wave bands so as to respectively enhance the light absorption of ultraviolet, visible and near infrared wave bands and realize the discrimination and selective strong absorption of the ultraviolet, visible and near infrared wave bands.
The differential evaluation detection of the main unit and the base unit (3D CNTs-G without any nano crystal grain modified) of the selective strong absorption array of each waveband can avoid the change of sensitivity caused by different areas of the absorption material. And due to the excellent characteristics and differential detection of the 3D CNTs-G, the device can be miniaturized and developed and has ultrahigh sensitivity.
The grating voltage switch can be used for randomly switching and detecting ultraviolet, visible and near-infrared light waves and simultaneously detecting ultraviolet to near-infrared light waves.
The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (8)
1. The preparation method of the graphene-carbon nanotube three-dimensional compound is characterized by comprising the following steps of:
step 1: preparation of the chemical phthalocyanine iron and growth substrate: cutting a growth substrate silicon wafer, ultrasonically cleaning the silicon wafer in acetone, ethanol and deionized water, drying the silicon wafer, placing the silicon wafer on a quartz boat, and then placing phthalocyanine iron powder on the silicon wafer substrate;
step 2: the quartz boat is arranged in the reaction chamber of the quartz tube: pushing the quartz boat to the edge of the heating furnace to prevent the phthalocyanine iron from being pushed into the heating furnace to sublimate in advance;
and step 3: introducing argon and starting heating: opening a protective gas argon gas cylinder valve, opening a gas flow instrument, setting the gas flow instrument to be 60sccm, starting to heat the heating furnace, wherein the target temperature is 900 ℃, and the heating rate is set to be 0.5 ℃/s;
and 4, step 4: introducing hydrogen: opening a valve of a hydrogen gas bottle, setting the hydrogen flow of a gas flowmeter to be 10sccm, wherein at the moment, the phthalocyanine iron does not reach the sublimation temperature at the pipe orifice of the heating furnace, moving the phthalocyanine iron to a sublimation temperature area after the hydrogen in the pipe is filled in the whole quartz pipe, and beginning sublimation of the phthalocyanine iron after the hydrogen completely reaches a silicon substrate growth area, so that the next operation is started after the hydrogen is introduced for 10 minutes;
and 5: moving the quartz boat to a growth temperature region: the quartz tube is pushed at a speed of 1cm/min, phthalocyanine iron can be seen to be sublimated into black green gas in the pushing process, and the temperature in the furnace is slightly reduced;
step 6: growing the graphene-carbon nanotube three-dimensional compound: after the quartz tube is pushed, phthalocyanine iron is in a high-temperature area in the furnace at the moment, is rapidly sublimated, cracked and vaporized, a silicon wafer substrate for growing the carbon nano tube is also in the growth temperature area, under the action of reducing hydrogen and catalyst iron particles, a graphene-carbon nano tube three-dimensional compound starts to be generated on the silicon wafer substrate, the hydrogen is turned off after 15 minutes, and heating is stopped;
and 7: cooling: gradually cooling the furnace under the protection of argon, naturally cooling the furnace for 3 hours to room temperature, and still introducing protective gas argon in the whole process of cooling the furnace to prevent the graphene-carbon nanotube three-dimensional compound from being oxidized at high temperature;
and 8: taking out the graphene-carbon nanotube three-dimensional compound: and when the heating furnace is cooled to room temperature, closing the argon and the gas flowmeter, opening the gas inlet end of the quartz tube, pulling out the quartz boat, and then, observing that the silicon substrate on the quartz boat is changed into grey white, wherein the grey white is the graphene-carbon nanotube three-dimensional compound.
2. The method for preparing a graphene-carbon nanotube three-dimensional composite according to claim 1, wherein: in the step 1, the ultrasonic cleaning time is 10 minutes, and phthalocyanine powder is regulated into a square of 2 multiplied by 2cm & lt 2 & gt and arranged between 2cm and 8cm away from the edge of the silicon wafer substrate.
3. The method for preparing a graphene-carbon nanotube three-dimensional composite according to claim 1, wherein: in the step 3, the holding time in the heating furnace is set to be 150 minutes; wherein the temperature in the heating furnace reaches 900 ℃, the temperature is increased at the speed of 0.5 ℃/s, the time is 30 minutes, the time for keeping the temperature in the heating furnace is at least 110 minutes in order to make the temperature more stable and continue for 20 minutes, and the time for growth is prolonged by experimental factors such as instruments, human beings and the like, and the time for keeping in the heating furnace is optimally set to be 150 minutes in order to have sufficient time and a proper growth environment.
4. The method for preparing a graphene-carbon nanotube three-dimensional composite according to claim 1, wherein: the quartz tube was advanced 6 cm in step 5 so that both the phthalocyanine iron and the silicon substrate were within the specified location area.
5. The method for preparing the graphene-carbon nanotube three-dimensional composite according to any one of claims 1 to 4, wherein: the heating furnace is heated by a temperature control system.
6. The method for preparing a graphene-carbon nanotube three-dimensional composite according to claim 1, wherein: and 8, taking down the silicon wafer on which the graphene-carbon nanotube three-dimensional compound grows by using tweezers, cleaning the quartz boat by using an alcohol cotton ball, placing the quartz boat in a specified position, and cleaning the test bed and the instrument and equipment.
7. The application of the graphene-carbon nanotube three-dimensional compound is characterized in that: the graphene-carbon nanotube three-dimensional compound is applied to a selective ultrafast photoelectric detector.
8. The use of the graphene-carbon nanotube three-dimensional composite according to claim 7, wherein: the compound is a light absorption material and a 3D transmission channel of a current carrier, and the graphene-carbon nano tube is modified with nanocrystalline grains with strong absorption at different wave bands so as to increase the absorption difference of each wave band; then preparing an ultraviolet, visible and near-infrared band selective strong absorption array unit with an FET structure, and finally integrating all band detection units on the same silicon substrate.
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